JPH0623867B2 - Color image forming method and developer particles for developing electrostatic latent image - Google Patents

Color image forming method and developer particles for developing electrostatic latent image

Info

Publication number
JPH0623867B2
JPH0623867B2 JP63311463A JP31146388A JPH0623867B2 JP H0623867 B2 JPH0623867 B2 JP H0623867B2 JP 63311463 A JP63311463 A JP 63311463A JP 31146388 A JP31146388 A JP 31146388A JP H0623867 B2 JPH0623867 B2 JP H0623867B2
Authority
JP
Japan
Prior art keywords
particles
color
image
color image
developing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP63311463A
Other languages
Japanese (ja)
Other versions
JPH02157768A (en
Inventor
長穂 細野
真吉 高橋
初雄 田嶋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Inc filed Critical Canon Inc
Priority to JP63311463A priority Critical patent/JPH0623867B2/en
Priority to US07/447,070 priority patent/US5045420A/en
Publication of JPH02157768A publication Critical patent/JPH02157768A/en
Publication of JPH0623867B2 publication Critical patent/JPH0623867B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/01—Electrographic processes using a charge pattern for multicoloured copies
    • G03G13/013—Electrographic processes using a charge pattern for multicoloured copies characterised by the developing step, e.g. the properties of the colour developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0926—Colouring agents for toner particles characterised by physical or chemical properties

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Color Electrophotography (AREA)

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は電子写真法乃至は静電記録法を用いたカラー画
像記録方法に関するもので、静電潜像を顕画粒子で現像
して得られた顕画像を露光してカラー画像を得るように
したカラー画像形成方法およびこのカラー画像形成方法
に用いる静電潜像現像用顕画粒子に関する。TECHNICAL FIELD The present invention relates to a color image recording method using electrophotography or electrostatic recording, which is obtained by developing an electrostatic latent image with visible particles. The present invention relates to a color image forming method for exposing the obtained visible image to obtain a color image, and the developing particles for developing an electrostatic latent image used in the color image forming method.

〔従来の技術〕[Conventional technology]

従来、電子写真法乃至は静電記録法を用いたカラー画像
記録方法では、必要とする色の数だけの種類の現像剤と
必要とする色の数だけの種類の現像器とが必要であっ
た。例えば多色カラーではその色の数だけ、ピクトリア
ル・カラーではＣ・Ｍ・ＹまたはＣ・Ｍ・Ｙ・Ｂｋの３
〜４種類が必要であった。また（潜像形成工程・現像工
程・転写工程）を、多色カラーではその色の数だけ、ピ
クトリアル・カラーでは３〜４回、繰り返す必要があっ
た（以下、多重転写記録法）。また、特許公開公報昭和
63-139374号報、米国特許4,654,282号報等に開示されて
いるように（潜像工程・現像工程）を潜像形成体上で、
多色カラーではその色の数だけ、ピクトリアル・カラー
では３〜４回重ねて繰り返す（必要であればその後、転
写紙に転写する）必要があった（以下、多重現像記録
法）。Conventionally, in a color image recording method using an electrophotographic method or an electrostatic recording method, it is necessary to have a developer of the number of kinds of required colors and a developing device of the number of kinds of required colors. It was For example, in the case of multicolored colors, the number of colors is the same, and in the case of pictorial colors, C, M, Y or C, M, Y, Bk
~ 4 types were needed. Further, the (latent image forming step, developing step, and transfer step) had to be repeated for the number of colors in multicolor and three to four times in pictorial color (hereinafter, multiple transfer recording method). Also, the patent publication Gazette Showa
As disclosed in 63-139374, U.S. Pat. No. 4,654,282, etc. (latent image step / developing step) on a latent image forming body,
In the case of multicolored colors, it was necessary to repeat the same number of times as in the case of pictorial color, and to repeat it 3 to 4 times (transferred to transfer paper if necessary) (hereinafter, multiple development recording method).

このために、多重転写記録法では複数回転写により、多
重現像記録法では現像後の潜像形成により、現像された
顕画像の乱れが生じてしまう。Therefore, in the multiple transfer recording method, a plurality of transfers are performed, and in the multiple development recording method, a latent image is formed after development, so that the developed visible image is disturbed.

また、記録装置内に多数の現像器を設置しなければなら
ず、必要な占有スペースが大きくなり、これにともなっ
て記録装置も大きくなり、小型化が困難であった。In addition, a large number of developing devices have to be installed in the recording apparatus, and the required occupying space becomes large, and accordingly, the recording apparatus also becomes large, and downsizing is difficult.

また、米国特許第4,725,527号明細書には異なる波長の
光を吸収してそれぞれ消色する複数種の感受性粒子を含
有する記録層に選択された波長の光を選択された部位に
照射して感受性粒子を選択的に消色させてカラー画像を
形成する方法が提案されている。この方法は、複数回の
露光、即ち、赤、緑および青の３回露光だけでカラー画
像を現像できる点で優れている。しかし、記録媒体とし
て紙の表面に感受性粒子を均一に塗布したものが必要と
されるから、記録媒体として普通紙を使用することはで
きない。また、記録媒体の表面の一部分にカラー画像を
形成する場合にも、それ以外の部分についても消色に必
要な光エネルギーによる３回露光を行って白色にする必
要があるので画像形成に時間を要する。Further, U.S. Pat.No. 4,725,527 describes that a recording layer containing a plurality of types of sensitive particles that absorbs light of different wavelengths and decolors them respectively is irradiated with light of a selected wavelength to a selected portion. A method of selectively erasing particles to form a color image has been proposed. This method is excellent in that a color image can be developed only by multiple exposures, that is, three exposures of red, green and blue. However, it is not possible to use plain paper as a recording medium, since a recording medium having sensitive particles uniformly coated on the surface is required. Further, even when a color image is formed on a part of the surface of the recording medium, it is necessary to expose the other part to white by performing three times of exposure with light energy required for decoloring. It costs.

〔発明が解決しようとする問題点〕[Problems to be solved by the invention]

本発明は、従来の方法が有していた上記問題点を解決し
たカラー画像形成方法およびこの方法に用いる静電潜像
現像用顕画粒子を提供することを目的としている。さら
に詳しく述べるならば、 （１）変動要因の多いプロセス工程の回数（帯電回数、
潜像形成回数、転写回数、現像回数等）及現像剤の種類
の数を減少させることにより、どのような環境において
も常に安定したカラー画像形成方法を提供する。SUMMARY OF THE INVENTION It is an object of the present invention to provide a color image forming method which solves the above problems of the conventional method, and an electrostatic latent image developing developer particle used in this method. More specifically, (1) the number of process steps with many fluctuation factors (number of charging times,
The number of latent image formations, the number of transfers, the number of developments, etc.) and the number of types of developers are reduced to provide a stable color image forming method in any environment.

（２）特に多数の現像器を記録装置内に設置しなくても
よい、小型化が可能なカラー画像形成方法を提供するこ
とにある。(2) An object of the present invention is to provide a color image forming method which can be downsized without particularly requiring a large number of developing devices to be installed in the recording apparatus.

（３）また、普通紙に高速でカラー画像を形成できるカ
ラー画像形成方法を提供することにある。(3) Another object of the present invention is to provide a color image forming method capable of forming a color image on plain paper at high speed.

（４）また、上記（１）〜（３）のカラー画像形成方法
に有用な静電潜像現像用顕画粒子を提供することにあ
る。(4) It is another object of the present invention to provide developer particles for developing an electrostatic latent image, which are useful in the color image forming methods described in (1) to (3) above.

〔発明が解決するための手段及び作用〕[Means and Actions for Solving the Invention]

本発明によるカラー画像形成方法は、異なる波長の光を
吸収してそれぞれ消色する複数種の感受性粒子を含有す
る顕画粒子により静電潜像を現像する工程および現像に
より得られる顕画像を、該感受性粒子を選択的に消色さ
せる波長の光で露光する工程を有することを特徴とする
ものである。The color image forming method according to the present invention comprises a step of developing an electrostatic latent image with developing particles containing a plurality of types of sensitive particles that absorb light of different wavelengths and decolor each, and a visible image obtained by the development. It is characterized in that it comprises a step of exposing the sensitive particles to light having a wavelength capable of selectively decoloring.

本発明によるカラー画像形成方法は電子写真法または静
電記録方法などにより静電潜像を形成し、これを電子写
真法と同じようにして顕画粒子で現像した後に、顕画粒
子に含まれる複数種の感受性粒子を選択的に特定の波長
の光で露光することで複数種の感受性粒子を選択的に消
色させる。これによって顕画粒子の色を変化させてカラ
ー画像を形成できるものである。カラー画像が多色カラ
ー画像やピクトリアルカラーの場合には後述するように
複数の特定の波長による露光を顕画像に逐次又は同時に
行う必要があるが、現像工程は１回で済み、現像を複数
回行う場合の前記した如き問題点は解決される。また、
本発明によるカラー画像形成方法においては、顕画粒子
は静電潜像が形成されている電子写真感光体は静電潜像
保持部材に静電潜像上に選択的に付着し、この顕画粒子
像をカラー画像化した後に記録媒体に転写するものであ
るから画像保持材としては、普通紙，フィルム等の任意
のものを使用することができる。また、記録媒体の表面
の一部分にカラー画像を形成する場合にも、顕画粒子が
カラー画像形成部分にのみ存在するので、非画像部の消
色処理は不要になり、カラー画像形成プロセスを効率的
に行うことができるものである。また、本発明では、顕
画粒子を選択的に消色してカラー画像化するに際して、
消色位置を顕画粒子像の位置を基準に決めることができ
るので、紙の縁から消色位置を決める場合に較べて位置
精度を高めることができる。また、本発明では静電潜像
を顕画粒子で現像する際に、画像濃度に応じて顕画粒子
の付着量を制御できるから、消色による中間調処理を合
せて、中間調の再現が容易にできるものである。In the color image forming method according to the present invention, an electrostatic latent image is formed by an electrophotographic method, an electrostatic recording method, or the like, and the latent image is developed in the same manner as in the electrophotographic method. By selectively exposing the plurality of types of sensitive particles to light having a specific wavelength, the plurality of types of sensitive particles are selectively decolorized. As a result, the color of the visible particles can be changed to form a color image. When the color image is a multicolor image or a pictorial color image, it is necessary to sequentially or simultaneously expose the visible image with a plurality of specific wavelengths as described later, but the developing process is performed only once, and the developing process is performed in plural. The above-mentioned problems in the case of performing the operation once are solved. Also,
In the color image forming method according to the present invention, the electrophotographic photosensitive member on which the electrostatic latent image is formed by the image-forming particles is selectively attached to the electrostatic latent image holding member on the electrostatic latent image. Since the particle image is formed into a color image and then transferred to a recording medium, an arbitrary material such as plain paper or film can be used as the image holding material. Further, even when a color image is formed on a part of the surface of the recording medium, the image-developing particles are present only in the color image forming part, so that the decoloring process of the non-image part is not necessary and the color image forming process is efficiently performed. Is something that can be done. Further, in the present invention, in selectively erasing the visible particles to form a color image,
Since the erasing position can be determined on the basis of the position of the visualized particle image, the positional accuracy can be improved as compared with the case where the erasing position is determined from the edge of the paper. Further, in the present invention, when the electrostatic latent image is developed with the developer particles, the amount of the developer particles attached can be controlled according to the image density. Therefore, halftone processing by erasing can be combined to reproduce the halftone. It can be done easily.

なお、記録媒体自体が静電潜像を保持できるものである
場合には、顕画粒子像の転写工程を省くことができる。If the recording medium itself can hold the electrostatic latent image, the step of transferring the visible particle image can be omitted.

第１図〜第５図及第１表〜第２表は本発明の実施例を示
すもので、第１図は本発明のカラー画像記録方法を示す
装置の概略図であり、第２図はその光学系ユニットの例
を示し、第３図はその光学系ユニットに組み込まれたカ
ラー露光光源の例を示し、第４図は複数の波長の光にそ
れぞれ感度を有する感受性粒子をいっしょに含有する顕
画粒子を示し、第５図はその顕画粒子を用いた現像装置
を示す。また、第１表は第１図に示した像露光光源とカ
ラー露光光源との組み合わせの例を示し、第２表は顕画
粒子内にいっしょに含有する複数の波長の光に、それぞ
れ感度を有する感受性粒子を作るときに用いるそれぞれ
の波長の光に感度を有する顕画粒子を示している。1 to 5 and Tables 1 and 2 show embodiments of the present invention, FIG. 1 is a schematic view of an apparatus showing a color image recording method of the present invention, and FIG. Fig. 3 shows an example of the optical system unit, Fig. 3 shows an example of a color exposure light source incorporated in the optical system unit, and Fig. 4 together contains sensitive particles sensitive to light of a plurality of wavelengths. The visible particles are shown, and FIG. 5 shows a developing device using the visible particles. Table 1 shows an example of the combination of the image exposure light source and the color exposure light source shown in FIG. 1, and Table 2 shows the sensitivity to light of a plurality of wavelengths contained together in the developer particles. 3 shows the visible particles that are sensitive to light of each wavelength used when making the sensitive particles.

第１図及第２図において、１は電子写真感光体、２は帯
電器、３−１は像露光光学系ユニットを示し、４はでき
た静電潜像を現像する現像器、３−２はできた顕画粒子
像を露光して変色させカラー画像を得るためのカラー露
光光学系ユニット。５は給紙手段、６は転写手段、７は
記録紙で、変色させて得られたカラー顕画粒子像を記録
紙７上に転写する。８は熱ローラー定着器等の熱定着器
で得られたカラー顕画粒子像を記録紙７上に熱定着固定
・安定化する。９はクリーニング手段である。In FIGS. 1 and 2, 1 is an electrophotographic photosensitive member, 2 is a charger, 3-1 is an image exposure optical system unit, 4 is a developing device for developing the electrostatic latent image formed, 3-2 A color exposure optical system unit for exposing a developed particle image to change its color to obtain a color image. Reference numeral 5 is a paper feeding means, 6 is a transfer means, and 7 is a recording paper, and the color visualized particle image obtained by changing the color is transferred onto the recording paper 7. A color fixing particle image 8 obtained by a heat fixing device such as a heat roller fixing device is fixed and stabilized by heat fixing on the recording paper 7. 9 is a cleaning means.

像露光光学系ユニット３−１は例えば第２図に示すレー
ザ走査光学系で、光学系ユニット３内の露光光源３１が
１種類の波長光源の場合を示す。３１は露光光源、３２
はポリゴミ・ミラー、３３はｆθレンズ等のレンズ・ユ
ニットである。カラー露光光学系ユニット３−２として
は例えば第２図に示すレーザ光学系で、光学系ユニット
３内の露光光源３１が波長の異なる３種類のＲＧＢ波長
光源となっているものが用いられる。この場合、３種類
の波長の異なるＲＧＢのそれぞれの波長を有する光源
が、第３図に示すように、主走査方向に配列させた場合
31-1と、副走査方向に配列させた場合31-2があるが、そ
のどちらでも良い。レーザでＲ（赤）光源を得るには例
えばHe-Neレーザを、Ｇ（緑）光源とＢ（青）光源とを
得るには例えばArレーザを用いれば良い。The image exposure optical system unit 3-1 is, for example, the laser scanning optical system shown in FIG. 2, and shows the case where the exposure light source 31 in the optical system unit 3 is one type of wavelength light source. 31 is an exposure light source, 32
Is a poly dust mirror, and 33 is a lens unit such as an fθ lens. As the color exposure optical system unit 3-2, for example, a laser optical system shown in FIG. 2 in which the exposure light source 31 in the optical system unit 3 is three kinds of RGB wavelength light sources having different wavelengths is used. In this case, three types of light sources having different RGB wavelengths are arranged in the main scanning direction as shown in FIG.
There are 31-1 and 31-2 when arranged in the sub-scanning direction, but either one may be used. A He-Ne laser may be used to obtain an R (red) light source with a laser, and an Ar laser may be used to obtain a G (green) light source and a B (blue) light source.

なお、像露光光学系ユニット３−１とカラー露光光学系
ユニット３−２は第２図に示すレーザ光学系である必要
はなく、その光源もＬＥＤでもカラー・フイルター付の
ＬＣＳ（液晶シヤツター光源）でもＬＤ（レーザ・ダイ
オード光源）でも良い。この組み合わせは第１表に示す
組み合わせ等が挙げられる。The image exposure optical system unit 3-1 and the color exposure optical system unit 3-2 do not have to be the laser optical system shown in FIG. 2, and the light source can be an LED or an LCS (liquid crystal shutter light source) with a color filter. However, it may be an LD (laser diode light source). Examples of this combination include those shown in Table 1.

本発明は、電子写真法乃至は静電記録法等によって作っ
た静電潜像をそれぞれの波長に感度を有する感受性粒子
を同一粒子内にいっしょに含有する顕画粒子で現像し、
後にカラー露光して、カラー画像を得る方法であるが、
ここでは、電子写真法を用いた方法を例にして説明す
る。静電記録法を用いるときは、電子写真感光体１の代
りに静電記録体を像露光光学系ユニット３−１の代りに
静電記録ヘッドを用いれば良い。この場合、帯電器２は
静電記録体上を一定の電位に保つ機能があれば良いが、
静電記録体を繰り返し使用しないときは帯電器２は必ず
しも必要ではない。 The present invention is to develop an electrostatic latent image produced by electrophotography or electrostatic recording method or the like with developing particles containing together sensitive particles having sensitivity to each wavelength in the same particle,
It is a method to obtain a color image by color exposure afterwards,
Here, a method using electrophotography will be described as an example. When the electrostatic recording method is used, an electrostatic recording body may be used instead of the electrophotographic photosensitive member 1 and an electrostatic recording head may be used instead of the image exposure optical system unit 3-1. In this case, it suffices for the charger 2 to have a function of maintaining a constant potential on the electrostatic recording body.
The charger 2 is not always necessary when the electrostatic recording body is not repeatedly used.

電子写真感光体１の表面を帯電器２で一定の電位に帯電
し、像露光光学系ユニット３−１（ここではレーザ走査
光学系ユニツト）で像様に電子写真感光体１の表面を露
光し、これにより電位減衰した領域の電子写真感光体１
の表面に、電子写真感光体１の帯電極性と同じ極性に帯
電した顕画粒子41を現像器４によって付着させ現像す
る。このためには、第５図に示すように、現像ローラー
42に厚さ２〜４mmのゴム板等の弾性塗布ブレード43を現
像ローラー42の回転方向に対してカウンターになるよう
にその先を（エツジ部を避けて）圧接させ、表面が顕画
粒子41の個数平均粒径以下の粗さに粗らした現像ローラ
ー42を図示した矢印の方向に回転することによって、顕
画粒子41の層を厚さ約120μｍで現像ローラー42上に形
成する。また、電子写真感光体１の電位減衰した領域に
同極性に帯電した顕画粒子を付着現像させるために、現
像ローラー42を電子写真感光体１の背面電極に対して電
子写真感光体１の帯電極性側に現像バイアスをシフトさ
せて現像する。即ち、直流電圧印加または交番電圧に直
流電圧を重畳させた電圧等の交互電圧を印加等シフトさ
せた電圧を印加して現像すれば良い。例えば直流電圧印
加では、電子写真感光体１の帯電電圧とほぼ同等以下の
電圧を印加し、交互電圧印加では、上記直流電圧に周波
数が400Hzから３KHz、Vppが800Vpp〜22KVpp程度の交流
電圧を印加すればよい。Vppはピークトウピーク電圧で
ある。The surface of the electrophotographic photosensitive member 1 is charged to a constant potential by the charger 2, and the surface of the electrophotographic photosensitive member 1 is imagewise exposed by the image exposure optical system unit 3-1 (here, the laser scanning optical system unit). , The electrophotographic photosensitive member 1 in the region where the potential is attenuated by this
The developer particles 4 are attached to the surface of the electrophotographic photosensitive member 1 by the developing device 4 to develop the particles 41, which are charged to the same polarity as the charging polarity of the electrophotographic photosensitive member 1. To this end, as shown in FIG.
An elastic coating blade 43 such as a rubber plate having a thickness of 2 to 4 mm is pressed against 42 so as to act as a counter to the rotation direction of the developing roller 42 (avoid the edge portion), and the surface of the visible particle 41 By rotating the developing roller 42 roughened to a roughness not more than the number average particle diameter in the direction of the arrow shown in the drawing, a layer of the visible particles 41 is formed on the developing roller 42 with a thickness of about 120 μm. Further, in order to attach and develop the developer particles charged with the same polarity to the region of the electrophotographic photosensitive member 1 where the potential is attenuated, the developing roller 42 is charged with respect to the back electrode of the electrophotographic photosensitive member 1 to charge the electrophotographic photosensitive member 1. Development is performed by shifting the development bias to the polar side. That is, development may be performed by applying a DC voltage or applying a voltage obtained by shifting an alternating voltage such as a voltage obtained by superimposing a DC voltage on an alternating voltage. For example, when applying a DC voltage, a voltage that is substantially equal to or lower than the charging voltage of the electrophotographic photosensitive member 1 is applied, and when applying an alternating voltage, an AC voltage having a frequency of 400 Hz to 3 KHz and a Vpp of about 800 Vpp to 22 KVpp is applied to the DC voltage. do it. Vpp is the peak to peak voltage.

次に現像された顕画粒子像をカラー露光光学系ユニツト
３−２によって露光し、顕画粒子像を変色させることに
よってカラー画像を得る。Next, the developed particle image is exposed by the color exposure optical system unit 3-2 to change the color of the particle image to obtain a color image.

カラー露光光学系ユニツト３−２による露光位置が目標
の顕画粒子像の位置とずれないためには、像露光光学系
ユニット３−１による露光と、カラー露光光学系ユニツ
ト３−２による露光と同期を精度良くとればよい。ま
た、像露光光学系ユニット３−１による静電潜像を現像
器４によって現像して得た顕画粒子像をCCD等のセンサ
ーにより検知してカラー露光光学系ユニツト３−２によ
って露光するタイミングを決定するようにしても良い。In order that the exposure position by the color exposure optical system unit 3-2 does not shift from the position of the target image particle image, the exposure by the image exposure optical system unit 3-1 and the exposure by the color exposure optical system unit 3-2 are performed. The synchronization should be accurate. Also, the timing at which a visible particle image obtained by developing the electrostatic latent image by the image exposure optical system unit 3-1 by the developing device 4 is detected by a sensor such as CCD and exposed by the color exposure optical system unit 3-2. May be determined.

第４図は複数の波長の光にそれぞれ感度を有する感受性
粒子41-1，41-2，41-3をいっしょに含有する顕画粒子41
の模式図を示したものである。ここで41-11，41-21およ
び41-31は酸化亜鉛(ZnO)、酸化チタン(TiO2)、ポリビニ
ール・カルバゾール(PVK)等の半導電性粒子である。41-
12，41-22および41-32は異なる波長の光にそれぞれ感度
を有する少なくともスピロピラン金属錯体を含む層で、
半導電性粒子41-11，41-21および41-31の表面に固定し
たスピロピラン金属錯体の層か又は親水性樹脂とスピロ
ピラン金属錯体とから成る層である。41-4は結着材で、
異なる波長にそれぞれ感度を有する上記感受性粒子41-
1，41-2および41-3を同時にそのなかに含有し、顕画粒
子41を形成している。FIG. 4 shows a visible particle 41 containing together sensitive particles 41-1, 41-2, 41-3 having sensitivity to light of a plurality of wavelengths.
It is a schematic diagram of. Here, 41-11, 41-21 and 41-31 are semiconductive particles such as zinc oxide (ZnO), titanium oxide (TiO 2 ), and polyvinyl carbazole (PVK). 41-
12, 41-22 and 41-32 are layers containing at least a spiropyran metal complex having sensitivity to light of different wavelengths,
It is a layer of spiropyran metal complex fixed on the surface of the semiconductive particles 41-11, 41-21 and 41-31 or a layer composed of a hydrophilic resin and a spiropyran metal complex. 41-4 is a binder,
The above-mentioned sensitive particles 41- each having sensitivity to different wavelengths
1, 41-2 and 41-3 are simultaneously contained therein to form visible particles 41.

ここで親水性樹脂としてはポリビニルブチラール、ポリ
ビニルホルマール、ポリビニルアルコール、ポリビニル
ピロリドン、エチルセルロース、メチルセルロース等の
水域はアルコールに可溶な樹脂を用いる。Here, as the hydrophilic resin, polyvinyl butyral, polyvinyl formal, polyvinyl alcohol, polyvinylpyrrolidone, ethyl cellulose, methyl cellulose, and the like, which are soluble in alcohol in the water region, are used.

グリーン光に感度を有するスピロピラン金属錯体（感光
剤）、レツド光に感度を有するスピロピラン金属錯体
（感光剤）、ブルー光に感度を有するスピロピラン金属
錯体（感光剤）の例を次に示す。Examples of spiropyran metal complex (photosensitizer) having sensitivity to green light, spiropyran metal complex (photosensitizer) having sensitivity to red light, and spiropyran metal complex (photosensitizer) having sensitivity to blue light are shown below.

（グリーン光に感度を有する感光剤） 塩化コバルト1,3-ジメチル-3-イソプロピル-6′-ニトロスピロ錯体ナフテン 酸亜鉛1,3,3-トリメチル-7′-ニトロ-スピロ錯体ナフテン 酸鉛1,3,3-トリメチル-5-クロロ-5′-ニトロ-8′-メトキシ-スピロ錯体 塩化コバルト1,3,3-トリメチルインド-ル-ノナフトスピラン錯体 （ブルー光に感度を有する感光剤） 塩化チタン1,3,3-トリメチル-ニトロ-スピロ錯体 塩化亜鉛3,3′-ジメチル-6′-ニトロ-スピロ錯体 塩化アンチモン3メチル-6-ニトロ-スピロ錯体 （レツド光に感度を有する感光剤）ナフテン 酸バリウム1,3,3-トリメチル-ニトロ-スピロ錯体ナフテン 酸バリウム1,3,3-トリメチル-インドリノ-ベンゾピリロ-スピラン錯体 塩化水銀1-フエニル-3,3-ジメチル-6′-ニトロ-8′-メトキシ-スピロ錯体 これらは半導電性粒子41-11，41-21，41-31の表面に固
定され、感光性の波長光の照射によって生じた電子が有
効に作用して、次々と連鎖反応を起こし、その波長に感
度を有する感受性粒子41-1，41-2，41-3のもともとの色
（シアン、マゼンタ、イエロー）が選択的に消色ないし
減色し、所望のカラー色が顕画粒子41に詳しくは顕画粒
子像に発現する。なお，多色画像記録を望む場合は感受
性粒子41-1，41-2，41-3のもともとの色は必ずしもシア
ン，マゼンタ，イエローである必要はないことは言うま
でもない。(Photosensitizer sensitive to green light) Cobalt chloride 1,3-Dimethyl-3-isopropyl-6'-nitrospiro complex Zinc naphthenate 1,3,3-Trimethyl-7'-nitro-spiro complex Lead naphthenate 1, 3,3-Trimethyl-5-chloro-5'-nitro-8'-methoxy-spiro complex Cobalt chloride 1,3,3-Trimethylindole-nonaphthopyran complex (photosensitizer sensitive to blue light) Titanium chloride 1 , 3,3-Trimethyl-nitro-spiro complex Zinc chloride 3,3'-Dimethyl-6'-nitro-spiro complex Antimony chloride 3-methyl-6-nitro-spiro complex (photosensitizer sensitive to red light) Naphthenic acid Barium 1,3,3-trimethyl-nitro-spiro complex Naphthenate Barium 1,3,3-trimethyl-indolino-benzopyrrilo-spirane complex Mercury chloride 1-phenyl-3,3-dimethyl-6′-nitro-8′- Methoxy-spiro complex These are semi-conductive particles 41-11, 41-21, 41 -31-41, 41-2, 41, which are fixed on the surface of -31, are effectively affected by electrons generated by irradiation with light having a photosensitive wavelength, and cause chain reactions one after another to have sensitivity at that wavelength. The original color (-3, cyan, magenta, yellow) of -3 is selectively erased or reduced, and a desired color appears on the developer particles 41, specifically, on the developer particle image. Needless to say, the original colors of the sensitive particles 41-1, 41-2, 41-3 need not necessarily be cyan, magenta, and yellow when a multicolor image recording is desired.

〔実施例１〕 （感受性粒子製法） スピロピラン塩化亜鉛とを少量のメタノール液中に溶解
させ、開環したスピロピランに金属がついた感光剤であ
るスピロピラン金属錯体（塩化亜鉛−3,3′−ジメチル
−６′−ニトロ−スピロ錯体）を形成させる。次に，こ
の液中に親水性樹脂としてポリビニルアルコール樹脂を
溶解させる。この液中に半導電性粒子として酸化チタン
粉体を混入し、充分ボールミルで攪拌した後、さらにこ
の液中に充分な量の石油系炭化水素分散液を入れた後、
もう一度ボールミルで攪拌する。このことによって，ス
ピロピラン金属錯体層を親水性樹脂と共に、半導電性粒
子の酸化チタン粉体粒子の表面に充分かつ適当な厚さで
層形成させる。この後ペーパーフイルターで濾過し、乾
燥させ、スピロピラン金属錯体層を充分かつ適当な厚さ
で表面に固定した個数平均粒径が約１μｍの半導電性粒
子の酸化チタン粉体（ブルー光に感度を有する感光性粉
体）を得る。[Example 1] (Method for producing sensitive particles) Spiropyran zinc chloride was dissolved in a small amount of a methanol solution, and a spiropyran metal complex (zinc chloride-3,3'-dimethyl) as a photosensitizer in which a metal was attached to a ring-opened spiropyran -6'-nitro-spiro complex) is formed. Next, a polyvinyl alcohol resin as a hydrophilic resin is dissolved in this liquid. Titanium oxide powder was mixed as semiconductive particles into this liquid, and after sufficiently stirring with a ball mill, after further adding a sufficient amount of petroleum hydrocarbon dispersion liquid to this liquid,
Stir in the ball mill again. As a result, the spiropyran metal complex layer is formed together with the hydrophilic resin on the surface of the titanium oxide powder particles of the semiconductive particles in a sufficient and appropriate thickness. After that, it is filtered with a paper filter and dried, and the spiropyran metal complex layer is fixed on the surface with a sufficient and appropriate thickness. Titanium oxide powder of semiconductive particles with a number average particle size of about 1 μm (sensitivity to blue light To have a photosensitive powder).

同様に，グリーン光に感度を有する酸化チタン粉体を核
にした感光性粉体及レツド光に感度を有する酸化チタン
粉体を核にした感光性粉体を感光剤を用いて、親水性樹
脂としてポリビニルアルコール樹脂と共に酸化チタン粉
体の表面を被覆して作成した。グリーン光に感度を持つ
感光剤としては、塩化コバルト1,3−ジメチル−３−イ
ソプロピル−６′−ニトロスピロ錯体を、またレツド光
に感度を持つ感光剤としては、ナフテン酸バリウム1,3,
3−トリメチル−ニトロ−スピロ錯体を用いた。Similarly, a photosensitive powder having a titanium oxide powder having a sensitivity to green light as a core and a photosensitive powder having a titanium oxide powder having a sensitivity to a red light as a core are used as a hydrophilic resin. Was prepared by coating the surface of titanium oxide powder with a polyvinyl alcohol resin. As a photosensitizer sensitive to green light, cobalt chloride 1,3-dimethyl-3-isopropyl-6'-nitrospiro complex, and as a photosensitizer sensitive to red light, barium naphthenate 1,3,
A 3-trimethyl-nitro-spiro complex was used.

（顕画粒子の製造） 水ないしアルコールに不溶な架橋性ポリマー（重合開始
剤を含む）溶液中に上記３種類の感光性粉体を混入し、
攪拌してエマルジヨンを作成する。半導電性粒子の表面
の感光層は親水性であるから、この水ないしアルコール
に不溶な感光層は架橋性ポリマー溶液中で溶解せずに安
定に保たれている。詳細なエマルジヨンの内訳は ポリエンカビニル 2.5ｇ シクロヘキサン 32.5ｇ トルエン 5.0ｇ 熱架橋性不飽和ポリエステル 5.0ｇ ベンゾール・パーオキサイド 0.1ｇ 燐酸トリブチル 1.5ｇ グリーン光感光性粒子 12.0ｇ ブルー光感光性粒子 12.0ｇ レツド光感光性粒子 12.0ｇ 上記エマルジヨンを乾燥させた後、粉砕法によって個数
平均粒径が約12μｍの顕画粒子からなる顕画剤を得た。(Production of Visualized Particles) The above-mentioned three kinds of photosensitive powders are mixed in a solution of a crosslinkable polymer (including a polymerization initiator) insoluble in water or alcohol,
Stir to create emulsion. Since the photosensitive layer on the surface of the semiconductive particles is hydrophilic, the photosensitive layer insoluble in water or alcohol is not dissolved in the crosslinkable polymer solution and is kept stable. The detailed emulsion details are: polyencavinyl 2.5 g cyclohexane 32.5 g toluene 5.0 g heat-crosslinkable unsaturated polyester 5.0 g benzol peroxide 0.1 g tributyl phosphate 1.5 g green light-sensitive particles 12.0 g blue light-sensitive particles 12.0 g redd Photosensitive particles 12.0 g The emulsion was dried and then pulverized to obtain a developer consisting of developer particles having a number average particle diameter of about 12 μm.

この顕画粒子と流動性向上と帯電の安定性のため、シリ
カ微粒子を加えた顕画剤を用いて現像し、この後にカラ
ー露光することにより鮮明で原稿に忠実なカラー画像記
録が感光体上に得られた。この像を紙の上に転写し、熱
ローラー定着器８により熱架橋性ポリマー結着材41-4を
架橋し定着固定したカラー画像が得られた。In order to improve the fluidity of the developer particles and the stability of charging, the developer is developed using a developer containing silica fine particles, and then color exposure is performed to obtain a clear and faithful color image recording on the photoreceptor. Was obtained. This image was transferred onto paper, and the heat roller fixing device 8 crosslinked the heat-crosslinkable polymer binder 41-4 to fix and fix the color image.

なお、カラー露光が全くされなかった部分は黒色の画像
として得られた。In addition, a portion which was not subjected to color exposure was obtained as a black image.

〔実施例２〕 半導電性粒子（酸化チタン粉体）の表面に親水性樹脂を
用いずにスピロピラン金属錯体を単に吸着で付着させた
個数平均粒径が約１μｍ弱の感光性粉体を用い、実施例
１で記述したと同様に感光性エマルジヨンを作った。Example 2 Using a photosensitive powder having a number average particle diameter of about 1 μm, which is obtained by simply adsorbing a spiropyran metal complex on the surface of semiconductive particles (titanium oxide powder) without using a hydrophilic resin. A photosensitive emulsion was prepared as described in Example 1.

このエマルジヨンを実施例１と同様に乾燥し、粉砕して
個数平均粒径が約10μｍの顕画粒子からなる顕画剤を得
た。シリカを混合した顕画剤を用いて現像し、カラー露
光して鮮明カラー画像記録が得られた。This emulsion was dried and pulverized in the same manner as in Example 1 to obtain a developer consisting of developer particles having a number average particle size of about 10 μm. Development was performed using a developer mixed with silica, and color exposure was performed to obtain a clear color image record.

但し、親水性樹脂を用いずに、スピロピラン金属錯体層
を薄い厚みで半導電性粒子の表面に被覆したために、実
施例１よりカラー露光時の露光量を増加することによっ
て実施例１並の画像を得ることができた。However, since the surface of the semiconductive particles was coated with a thin thickness of the spiropyran metal complex layer without using a hydrophilic resin, the exposure amount at the time of color exposure was increased as compared with Example 1 to obtain an image similar to that of Example 1. I was able to get

なお、静電記録法等を用いる場合には静電記録紙等の上
に静電潜像を形成し、該顕画粒子で現像し、この顕画粒
子像をカラー露光した後、熱ローラ定着器等により顕画
粒子の熱架橋性ポリマー結着材を熱架橋して定着してカ
ラー画像記録を得ることもできる。When the electrostatic recording method or the like is used, an electrostatic latent image is formed on an electrostatic recording paper or the like, developed with the image-forming particles, and the image-forming particle image is color-exposed and then fixed with a heat roller. It is also possible to obtain a color image record by thermally cross-linking and fixing the heat-crosslinkable polymer binder of the visible particles with a container or the like.

〔発明の効果〕〔The invention's effect〕

（１）変動要因の多いプロセス工程の回数（帯電回数、
潜像形成回数、転写回数、現像回数等）及現像剤の種類
の数を減少させることにより、どのような環境において
も常に安定したカラー画像形成方法を提供できる。(1) Number of process steps with many fluctuation factors (number of times of charging,
By reducing the number of latent image formations, the number of transfers, the number of developments, etc.) and the number of types of developers, it is possible to provide a stable color image forming method in any environment.

（２）ページメモリーや多くのバツフア・メモリーが必
要でなくなるように、画像メモリーの減少が可能となる
カラー画像形成方法を提供できる。(2) It is possible to provide a color image forming method capable of reducing the image memory so that the page memory and many buffer memories are not required.

（３）特に多数の現像器を記録装置内に設置しなくても
よい、小型化が可能なカラー画像形成方法を提供でき
る。(3) It is possible to provide a color image forming method that can be downsized without particularly requiring a large number of developing devices to be installed in the recording apparatus.

（４）普通紙にカラー画像が形成でき、また、非画像部
の消色処理不要なカラー画像形成方法を提供できる。(4) It is possible to provide a color image forming method that can form a color image on plain paper and that does not require decoloring of non-image areas.

【図面の簡単な説明】[Brief description of drawings]

第１図は本発明によるカラー画像形成方法に用いる装置
の概略図である。 第２図は第１図に示される装置の光学系ユニツトの概略
図である。 第３図は第１図に示される装置のカラー露光光学系ユニ
ツトの概略図である。 第４図は本発明による静電潜像現像用顕画粒子の模式図
である。 第５図は本発明によるカラー画像形成方法に用いる現像
器の概略図である。 １…電子写真感光体、２…帯電器 3-1…像露光光学系ユニツト 3-2…カラー露光光学系ユニツト ４…現像器、５…給紙手段 ６…転写手段、７…記録紙 ８…熱定着器、９…クリーニング手段 41…顕画粒子 41-1，41-2および41-3…感受性粒子 41-4…結着材 41-11，41-21および41-31…半導電性粒子 41-12，41-22および41-32…スピロピラン金属錯体層FIG. 1 is a schematic view of an apparatus used for a color image forming method according to the present invention. FIG. 2 is a schematic diagram of an optical system unit of the apparatus shown in FIG. FIG. 3 is a schematic view of a color exposure optical system unit of the apparatus shown in FIG. FIG. 4 is a schematic view of developer particles for electrostatic latent image development according to the present invention. FIG. 5 is a schematic view of a developing device used in the color image forming method according to the present invention. DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photoreceptor, 2 ... Charging device 3-1 ... Image exposure optical system unit 3-2 ... Color exposure optical system unit 4 ... Developing device, 5 ... Paper feeding means 6 ... Transfer means, 7 ... Recording paper 8 ... Thermal fixing device, 9 ... Cleaning means 41 ... Visual particles 41-1, 41-2 and 41-3 ... Sensitive particles 41-4 ... Binder 41-11, 41-21 and 41-31 ... Semi-conductive particles 41-12, 41-22 and 41-32 ... Spiropyran metal complex layer

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｇ０３Ｇ 15/01 Ｂ (56)参考文献 特開 昭60−244978（ＪＰ，Ａ) 宮本 五郎「天然色写真」共立出版株式 会社（昭和31年３月31日発行）第94〜95ペ ージ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical indication location G03G 15/01 B (56) Reference JP-A-60-244978 (JP, A) Goro Miyamoto “Natural” Color Photo "Kyoritsu Publishing Co., Ltd. (Published March 31, 1936) Pages 94-95

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】異なる波長の光を吸収してそれぞれ消色す
る複数種の感受性粒子を含有する顕画粒子により静電潜
像を現像する工程および現像により得られる顕画像を、
該感受性粒子を選択的に消色させる波長の光で露光する
工程を有することを特徴とするカラー画像形成方法。1. A process of developing an electrostatic latent image by means of developing particles containing a plurality of types of sensitive particles capable of absorbing light of different wavelengths and erasing them, and a developing image obtained by the development.
A color image forming method comprising a step of exposing the sensitive particles to light having a wavelength that selectively erases the color. 【請求項２】異なる波長の光を吸収して、それぞれ消色
する複数種の感受性粒子を含有することを特徴とする静
電潜像現像用顕画粒子。2. Particles for developing an electrostatic latent image, comprising a plurality of types of sensitive particles that absorb light of different wavelengths and each decolorize.
JP63311463A 1988-12-09 1988-12-09 Color image forming method and developer particles for developing electrostatic latent image Expired - Lifetime JPH0623867B2 (en)

Priority Applications (2)

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JP63311463A JPH0623867B2 (en) 1988-12-09 1988-12-09 Color image forming method and developer particles for developing electrostatic latent image
US07/447,070 US5045420A (en) 1988-12-09 1989-12-07 Color image forming method and particulate developer for developing electrostatic latent image

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Application Number Priority Date Filing Date Title
JP63311463A JPH0623867B2 (en) 1988-12-09 1988-12-09 Color image forming method and developer particles for developing electrostatic latent image

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JPH02157768A JPH02157768A (en) 1990-06-18
JPH0623867B2 true JPH0623867B2 (en) 1994-03-30

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JPH02157768A (en) 1990-06-18
US5045420A (en) 1991-09-03

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